Quinyloxy-phenyloxy-oxime ester compounds having herbicidal activity

ABSTRACT

Oxime ester compounds of the formula    &lt;IMAGE&gt;  I  wherein A is one of the groups   &lt;IMAGE&gt;  wherein B is -CH= or nitrogen and R1 is one of the groups   &lt;IMAGE&gt;  wherein R2-R7, m and n are as hereinafter set forth, processes for their preparation, herbicidal compositions containing these compounds as the active ingredient and methods of use of the herbicidal compositions are disclosed.

SUMMARY OF THE INVENTION

The invention relates to oxime esters of the formula ##STR4## wherein Ais one of the groups ##STR5## in which R₂ signifies hydrogen, halogen ortrifluoromethyl and R₃ is hydrogen, halogen or trifluoromethyl, m is 1or 2, B is --CH═ or nitrogen, and wherein R₁ is one of the groups##STR6## wherein when A is a group of formula Ia or a group of formulaIb in which B is --CH═, R₄, R₅, R₆ and R₇ are lower alkyl, cycloalkylwith 3 to 6 carbon atoms, lower alkylcarbonyloxy-lower-alkyl, loweralkoxy or lower alkylthio or R₄ and R₅ or R₆ and R₇ together with thecarbon atom to which they are attached are a cycloalkyl group with 4 to7 carbon atoms and when B is nitrogen, R₆ and R₇ are as described above,R₄ and R₅ are lower alkylcarbonyloxy-lower-alkyl, lower alkoxy or loweralkylthio or R₄ is lower alkyl or cycloalkyl with 3 to 6 carbon atomsand R₅ represents lower alkylcarbonyloxy-lower-alkyl, lower alkoxy orlower alkylthio, wherein n is 1 or 2, and wherein R₄ and R₆ can also behydrogen.

In another aspect, the invention relates to herbicidal compositions andmethods.

DETAILED DESCRIPTION OF THE INVENTION

The invention is directed to oxime esters of the formula ##STR7##wherein A is one of the groups ##STR8## in which R₂ is hydrogen, halogenor trifluoromethyl and R₃ is hydrogen, halogen or trifluoromethyl, m is1 or 2, B is --CH═ or nitrogen, and wherein R₁ is one of the groups##STR9## wherein when A is a group of formula Ia or a group of formulaIb in which B is --CH═, R₄, R₅, R₆ and R₇ are lower alkyl, cycloalkylwith 3 to 6 carbon atoms, lower alkylcarbonyloxy-lower-alkyl, loweralkoxy or lower alkylthio or R₄ and R₅ or R₆ and R₇ together with thecarbon atom to which they are attached are a cycloalkyl group with 4 to7 carbon atoms and when B is nitrogen, R₆ and R₇ sare as describedabove, R₄ and R₅ are lower alkylcarbonyloxy-lower-alkyl, lower alkoxy orlower alkylthio or R₄ is lower alkyl or cycloalkyl with 3 to 6 carbonatoms and R₅ is lower alkylcarbonyloxy-lower-alkyl, lower alkoxy orlower alkylthio, and wherein n is 1 or 2 and wherein R₄ and R₆ can alsobe hydrogen.

The invention is also directed to processes for the preparation of thecompounds of formula I as well as herbicidal compositions which contain,as the active ingredient, a compound of formula I, and methods for theiruse. The compounds have both pre-emergence and post-emergence herbicidalactivity.

As used herein, the term "lower alkyl" encompasses both straight-chainand branched-chain hydrocarbon groups containing 1-6 carbon atoms suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl andthe like. Alkyl groups with 1-3 carbon atoms are preferred.

The term "halogen" encompasses fluorine, chlorine, bromine and iodine,and preferably chlorine and iodine.

Of the cycloalkyl groups with 3-6 or 4-7 carbon atoms, namelycyclopropyl, cyclobutyl, cyclypentyl, cyclohexyl and cycloheptyl,cyclohexyl is preferred.

In the lower alkoxy or lower alkylthio groups, the alkyl portion cancontain 1-6, preferably 1-3, carbon atoms.

Preferred compounds of formula I are those wherein A is the group Ib andB is --CH═. Further, there are preferred those compounds in which R₄,R₅, R₆ and R₇ represent alkyl groups with 1 or 2 carbon atoms,especially methyl.

Among the compounds of formula I, wherein A is the group Ib, wherein Bis --CH═, and R₁ is the group Ic, those compounds are preferred, whereinR₃ is different from hydrogen, i.e. wherein R₃ is halogen ortrifluoromethyl.

Preferred compounds of formula I are:

Acetone O-[2-[p-[[(6-chloro-2-quinolyl)oxy]phenoxy]-propionyl]oxime,

ethylO-[2-[p-[(6-bromo-quinolyl)oxy]phenoxy]-propionyl]acetohydroxamate,

[(isopropylideneamino)oxy]methyl2-[p-[(6-fluoro-2-quinolyl)oxy]phenoxy]propionate and

[(isopropylideneamino)oxy]methyl2-[p-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]propionate, especially theD-isomers of these compounds.

The compounds of formula I are prepared by one of the proceduresdescribed below.

A. Reacting an acid of the formula ##STR10## wherein A is as describedabove or a reactive derivative of this acid, with an oxime of theformula

    R.sub.4 R.sub.5 CNOH                                       III

wherein R₄ and R₅ are as described above.

The term "reactive derivative of the acid" encompasses an acid halide,especially the acid chloride, or an acid anhydride.

The esterification of an acid of formula II with an oxime of formula IIIis preferably carried out in a suitable inert solvent, especially atroom temperature or at an elevated temperature. A preferred temperaturerange is from about -10° to about +100° C., especially between 20° to70° C.

When an acid halide is used as the reactive derivative of the acid, thereaction with the oxime is carried out at room temperature and in thepresence of an acid acceptor, for example, a tertiary amine such aspyridine, triethylamine or the like, or in alkaline solution accordingto Schotten-Baumann. The corresponding ester is obtained in high yield.The acid chlorides are the preferred acid halides. The reaction ispreferably carried out in the presence of an inert solvent such asbenzene, toluene, petroleum ether or the like, or according toSchotten-Baumann in alkaline solution.

When the anhydride of the acid of formula II is used, the correspondingalkanecarboxylic acid ester of formula I can be prepared in high yieldby heating the anhydride with the oxime of formula III in the presenceof a base, preferably an alkali metal carbonate. Sodium carbonate isespecially preferred.

When a free acid of formula II is used as the starting material, thereaction with an oxime of formula III, is conveniently carried out inthe presence of dicyclohexylcarbodiimide. In carrying out this reaction,the acid of formula II is dissolved in an inert organic solvent such asa chlorinated hydrocarbon, for example, dichloromethane, chloroform,carbon tetrachloride, trichloroethane or the like, an ether, forexample, diethyl ether, diisopropyl ether, dioxan, or the like, anaromatic hydrocarbon, for example, benzene, toluene, xylene, or thelike, and thereafter the oxime of formula III is suspended in thissolution. The dicyclohexylcarbodiimide is dissolved in the same solventand the solution is added to the reaction mixture. The reaction iscarried out at a temperature between 0° and the boiling point of thereaction mixture, preferably between room temperature and 50°. Thereaction is completed after about 2 hours and the reaction mixture isfiltered. The filtrate is evaporated, and the residue is purified by,e.g. recrystallization or chromatography.

B. Reacting a compound of the general formula ##STR11## wherein Z is aleaving group and R₄, R₅, R₆ and R₇ are as described above,

with a compound of the formula ##STR12## wherein A is as describedabove, or an alkali metal salt thereof.

In formulas IV and V above, Z represents a leaving group, especiallychlorine, bromine, iodine, mesyloxy and tosyloxy. The leaving group mayalso be a reactive hydroxy group, especially a hydroxy group activatedby reaction with triphenylphosphine and azodicarboxylic acid or an esterthereof especially diethyl azodicarboxylate [see for example Bull. Chem.Soc. Japan 46, 2833 (1973) or Angew. Chem. 88, 111(1976)].

In accordance with this procedure, a compound of formula IV or V isreacted with a compound of formula VI or an alkali metal salt thereof ina manner known per se, and if required in the presence of a base. Thereaction is conveniently carried out in an inert organic solvent such asa hydrocarbon, for example, benzene, toluene, or the like, an ether, forexample diethyl ether, tetrahydrofuran, dimethoxyethane, orhexamethylphosphoric acid triamide or the like. The temperature andpressure are not critical and the reaction is preferably carried out ata temperature between -20° and the reflux temperature of the reactionmixture, preferably between -10° and 30° C.

Since the oxime ester compounds of formula I have asymmetric carbonatoms in the α-position to the carbonyl group, these compounds can existin optically active isomeric forms. In fact, these esters can have morethan one asymmetric carbon atom. The racemic compounds can be resolvedin their dextrorotatory and laevorotatory isomers using known proceduresas, for example, that described in Industrial and Engineering Chemistry60(8), 12-28 (1968). The racemic mixtures as well as the isomers allhave herbicidal activity with the D-isomer having the highest activityfollowed by the racemic mixture and the L-isomer. For example, it hasbeen found the the D-isomer of acetoneO-[2-[p-[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionyl]oxime has ahigher activity than the racemic mixture.

The isomers especially the D-isomers can also be prepared by synthesisfrom corresponding optically active starting materials.

In addition, and as a result of the nitrogen-carbon double bond in theoxime group ##STR13## it is also possible to have in each case twogeometric isomers when R₄ and R₅ or R₆ or R₇ are different. Theseisomers, the syn- and anti-form, can also be isolated in certain cases.

This invention is also directed to herbicidal compositions whichcomprise inert carrier material and, as the active ingredient, one ormore compounds of formula I. These herbicidal compositions suitablycontain, as the inert carrier material, at least one of the followingingredients: carrier materials, wetting agents, inert diluents andsolvents.

The compounds of formula I are, in general, water-insoluble. Thus, theusual methods of formulation of insoluble materials can be followed. Forexample, the compounds can be dissolved in a water-immiscible solventsuch as a high-boiling hydrocarbon which conveniently contains dissolvedemulsifiers so that the solution acts as a self-emulsifiable oil whenadded to water.

The compounds of formula I can also be mixed with a wetting agent, withor without an inert diluent, to form a wettable powder which is solubleor dispersible in water. The compounds can alternatively be mixed withan inert diluent to form a solid or pulverulent product.

Suitable inert diluents are solid inert media including pulverulent orfinely divided solids such as clays, sand, talc, mica, fertilizers andthe like. The resulting compositions can be either dusts or materials ofrelatively large particle size.

Wetting agents, suitable for use with the compounds of this invention,can be anionic, cationic or nonionic.

Examples of anionic wetting agents include soaps, fatty sulfate esterssuch as dodecyl sodium sulfate, octadecyl sodium sulfate and cetylsodium sulfate, fatty aromatic sulfonates such asalkylbenzene-sulfonates and butylnaphthalene-sulfonates, and the morecomplex fatty sulfonates such as the amide condensation products ofoleic acid and N-methyltaurine or the sodium sulfonate of dioctylsuccinate.

Examples of cationic wetting agents include cetyltrimethylammoniumbromide and the like.

Examples of nonionic wetting agents include, for example, condensationproducts of fatty acids, fatty alcohols or fatty substituted phenolswith ethylene oxides; fatty acid esters and ethers of sugars orpolyhydric alcohols; condensation products of sugars or polyhydricalcohols with ethylene oxide; and block copolymers of ethylene oxide andpropylene oxide.

The herbicidal compositions of this invention can also be used inaerosol form using, in addition to the propellant gas, carrier materialcomprising a co-solvent and a wetting agent. Suitable propellant gasesinclude the polyhalogenated alkanes such as dichlorodifluoromethane.

The herbicidal compositions of this invention can also contain otheractive ingredients such as synergistic agents, insecticides,bactericides, other herbicides, fungicides, plant growth regulators andfertilizers. Such combination preparations are suitable for increasingthe activity or for broadening the spectrum of activity.

The compounds of this invention are useful as both pre-emergent andpost-emergent herbicides. They are particularly suitable in combattingweed grasses such as slender foxtail (Alopecurus myosuroides) and typesof millet such as cock's foot (Echinochloa crus-galli), great foxtailmillet (Setaria faberii) and hair-like millet (Panicum capillare) incereals. They are suitable for use against these weed grasses especiallyin cereals such as barley, oats and wheat, and in rice, cotton, soya,sugar beet and vegetable crops. The compounds of this invention areespecially active against Alopecurus.

The pre-emergent and post-emergent herbicidal compositions of thisinvention are especially preferred for combatting weeds in sugar beetcrops. For example, acetoneO-[2-[p-[5-trifluoromethyl-2-pyridyl]oxy]phenoxy]propionyl]oxime appliedat a concentration of 1.25 kg/ha is sufficiently active against weedgrasses without damaging the sugar beet crop.

In general, the compounds of this invention are effective as herbicideswhen applied at a concentration of about 0.1 to about 6 kg/ha with thepreferred concentration range being from about 0.6 to about 2.0 kg/ha.An especially preferred application rate is from about 1 to about 1.5kg/ha.

The utility in corn crops of compounds of formula I wherein R₃ istrifluoromethyl is limited in cereal growing since these compounds aresomewhat phytotoxic. However, these compounds are particularly suitablefor combatting weed grasses in rice, cotton, soya, sugar beet andvegetable crops.

The herbicidal compositions of this invention can be in the form ofconcentrates suitable for storage or shipment. Such compositions cancontain, e.g. from about 2% to about 90% by weight, based on the weightof the total composition, of one or more of the active compounds of thisinvention. These concentrates can be diluted, with the same or differentinert carrier material, to concentrations which are suitable for actualuse. Ready-to-use compositions can contain concentrations of from 2% to80% by weight of the active ingredient. Particularly preferredconcentrations of active ingredients in the herbicidal compositions ofthis invention are from about 2% to about 80% by weight and preferablyfrom about 50% to about 80% by weight.

The following Examples illustrate the present invention.

EXAMPLE 1

3.4 g of 2-[p-[[(5-trifluoromethyl)-2-pyridyl]-oxy]phenoxy]propionicacid are suspended in 50 ml of dichloromethane and 1.1 g of acetoneoxime are added at room temperature. Thereafter, 2.1 g ofdicyclohexyl-carbodiimide, dissolved in 20 ml of dichloromethane, areadded dropwise over a period of 10 minutes; the temperature rises toabout 40° C. The mixture is stirred at room temperature for anadditional 2 hours. The mixture is filtered and the filtrate isevaporated to dryness on a rotary evaporator to yield acetoneO-[2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionyl]oxime;n_(D) ²⁴ 1.5202.

In an analogous manner compounds of formula I are prepared fromappropriate starting materials according to the procedure describedabove.

(1) D-2-[p-[(3-chloro-5-trifluoromethyl-2-pyridyl)-oxy]phenoxy]propionicacid and acetone oxime yield acetoneO-[D-2-[p-[(3-chloro-5-trifluoromethyl-2-pyridyl)oxy]phenoxy]propionyl]oxime; (2)D-2-[p-[[5-(trifluoromethyl)-2-pyridyl]-oxy]phenoxy]propionic acid andisopropylideneamino-oxy-ethanol yield 2-[(isopropylideneamino)oxy]-ethylD-2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]-propionate;

(3) D-2-[[5-(trifluoromethyl)-2-pyridyl]oxy]:-phenoxy]propionic acid and2-butanone oxime yield 2-butanoneO-[D-2-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionyl]oxime

(4) D-2-[[5-(trifluoromethyl)-2-pyridyl]oxy]-phenoxy]propionic acid andcyclohexanone oxime there is obtained cyclohexanoneO-[D-2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionyl]oxime.

The 2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]-phenoxy]propionic acidused as the starting material in the first paragraph of this Example canbe obtained as follows.

0.7 g of a 50% suspension of sodium hydride in mineral oil is washedtwice in an inert gas atmosphere with 5.0 ml of tetrahydrofuran eachtime. The washed suspension is added to 15.0 ml of tetrahydrofuran andtreated dropwise with a solution of 3.5 g ofp-[(5-trifluoromethyl-2-pyridyl)oxy]-phenol dissolved in 30.0 ml ofdimethylformamide. 3.5 g of ethyl L-2-[(p-tolylsulphonyl)oxy]propionatein 20.0 ml of dimethylformamide are subsequently added dropwise to themixture. The mixture is stirred at room temperature for an additional 12hours, thereafter poured onto ice and exhaustively extracted with ether.The extract is washed with water, dried over sodium sulphate andevaporated under reduced pressure. The residual ethylD-2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]-propionate can bepurified by adsorption on silica gel; [α]_(D) ²⁰ +21.7° (CHCl₃, c=1.1%).

5.3 g of ethylD-2-[p-[[5-(trifluoromethyl)-3-pyridyl]oxy]phenoxy]propionate aresuspended in 20 ml of methanol, treated with 1.7 g of potassiumhydroxide dissolved in 50 ml of water, and stirred at room temperaturefor 1.5 hours. For the working-up, the mixture is diluted with 200 ml ofwater, acidified with hydrochloric acid and extracted with ether. Theether extract is washed with water, dried over sodium sulphate andevaporated under reduced pressure. The residualD-2-[p-[[5-(trifluoromethyl)-2-pyridyl]oxy]oxy]phenoxy]propionic acidcan be purified by adsorption on silica gel; [α]_(D) ²² =+18.3° (CHCl₃,c=1.1%).

In an analogous manner, fromp-[(3-chloro-5-trifluoromethyl-2-pyridyl)oxy]-phenol and ethylL-2-[(p-tolylsulphonyl)oxy]propionate there is obtained ethylD-2-[p-(3-chloro-5-trifluoromethyl-2-pyridyl)oxy]phenoxy]propionate andtherefrom there is obtainedD-2-[p-[(3-chloro-5-trifluoromethyl-2-pyridyl)-oxy]phenoxy]propionicacid as well as the corresponding D-isomer of the oxime ester.

EXAMPLE 2

5.4 g of D-2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]-propionic acid and 2g of acetone oxime are dissolved in 30 ml of methylene chloride andtreated at room temperature with 3.2 g of dicyclohexylcarbodiimide. Inso doing, the temperature rises briefly to 34° C. After 20 minutes, themixture is filtered and the filtrate is evaporated. The residual oil ischromatographed on silica gel to yield 5.9 g of acetoneO-[D-2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]propionyl]oxime; [α]_(D) ²²=+67.9° (CHCl₃, c=1.3%).

The D-2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]-propionic acid used as thestarting material can be obtained as follows.

108 g of 4-(6-chloro-2-quinoyloxy)-phenol are dissolved with 110 g oftriphenylphosphine and 50 g of ethyl L-lactate in 200 ml ofN,N-dimethylformamide and treated slowly while cooling with 100 g ofdiisopropyl diazocarboxylate. The mixture is then extracted with waterand ether, the organic phase is dried and evaporated. The residual oilis chromatographed on silica gel with haxane/ether (1:2) to yield 100 gof methyl D-2[p-(6-chloro-2-quinolyloxy)phenoxy]propionate; [α]_(D) ²²=+28.8° (CHCl₃, c=1.8%).

80 g of the ester obtained according to the preceding paragraph areheated at 70° C. for 30 minutes in methanolic calcium hydroxide solution(40 g of calcium hydroxide in 400 ml of methanol). Thereupon, half ofthe methanol is removed by evaporation and the residue is extracted withwater and ether. The aqueous phase is acidified with phosphoric acid andthe product crystallizes out. The crystals are filtered off andrecrystallized from toluene/pentane to yield 60 g ofD-2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]propionic acid with a meltingpoint of 130° C.; [α]_(D) ²² =+15.6° (CHCl₃, c=1.72%).

EXAMPLE 3

In a manner analogous to Example 1 of 2, by reactingD-2-[[5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]-propionic acid withacetic acid ethyl ester oxime there is obtained ethyl3-[[[D-2-[[5-(trifluoromethyl)-2-pyridyl-oxy]phenoxy]propionyl]oxy]imino]butyrate.

EXAMPLE 4

1.76 g of [(isopropylideneamino)-oxy]methyl L(-)-lactate, 2.65 g oftriphenylphosphine and 2.72 g of p-[(6-chloro-2-quinoxalinyl)oxy]phenolare dissolved at 0° C. in 10 ml of absolute tetrahydrofuran. To theresulting solution, 1.75 g of diethylazodicarboxylate is added dropwisewith cooling and stirring. Thereafter the mixture is stirred for 1/2hour, poured into 100 ml of water and extracted twice with ethylacetate. The organic phase is washed with dilute hydrochloric acid andwater, dried over sodium sulfate and evaporated. The residue ischromatographed on 20 times its volume of silicagel using hexane/ethylacetate 8:2 as the eluant. The eluted product is recrystallized frommethylene chloride/n-hexane to yield [(isopropylideneamino)oxy]methylD-1-[p-[(6-chloro-2-quinoxalinyl)-oxy]-phenoxy]propionate. [α]_(D) ²⁰+20,05 (c=1.93% in CHCl₃) m.p. 75°-77° C.

In an analogous manner there is obtained from a 1:1 mixture ofp-[(6-fluoro-2-quinoxalinyl)oxy]phenol andp-[(7-fluoro-2-quinoxalinyl)-oxy]phenol, a 1:1 mixture of[(isopropylideneamino)oxy]methylD-1-[p-[(6-fluoro-2-quinoxalinyl)oxy]phenoxy]propionate and[(isopropylidene-amino)oxy]methylD-2-[p-[(7-fluoro-2-quinoxalinyl)oxy]phenoxy]propionate [α]_(D) ²²+21.18 (c=1.14% in CHCl₃).

EXAMPLE 5

An emulsifiable concentrate is prepared by mixing the followingingredients with one another:

    ______________________________________                                        Compound of formula I  500 g                                                  Condensation product of an alkyl-                                                                    100 g                                                  phenol and ethylene oxide; calcium                                            dodecylbenzenesulphonic acid                                                  Epoxidated soya oil with an oxirane                                                                   25 g                                                  oxygen content of about 6%                                                    Butylated hydroxytoluene                                                                              10 g                                                  ______________________________________                                    

The mixture is made up to 1 liter with xylene.

I claim:
 1. An oxime ester of the formula ##STR14## wherein A is##STR15## in which R₃ is hydrogen, halogen or trifluoromethyl, m is 1 or2, B is --CH═, and wherein R₁ is a group of the formula ##STR16##wherein R₆ and R₇ are lower alkyl, cycloalkyl with 3 to 6 carbon atoms,lower alkylcarbonyloxy-lower alkyl, lower alkoxy or lower alkylthio orR₆ and R₇ together with the carbon atom to which they are attached are acycloalkyl group with 3 to 7 carbon atoms, and wherein n is 1 or 2, andwherein R₆ can also be hydrogen.
 2. A compound according to claim 1,wherein R₆ and R₇ are lower alkyl, cycloalkyl with 3 to 6 carbon atoms,lower alkylcarbonyloxy-lower alkyl, lower alkoxy or lower alkylthio orR₆ and R₇ together with the carbon atom to which they are attached are acycloalkyl group with 4 to 7 carbon atoms and wherein n is 1 or
 2. 3. Acompound according to claim 1 or claim 2, wherein A is group Ib in whichB is --CH═.
 4. A compound according to claim 3, wherein R₁ is group Id.5. A compound according to claim 4, wherein R₆ and R₇ are alkyl groupswith 1 or 2 carbon atoms.
 6. A compound according to claim 5 wherein R₆,and R₇ are methyl.
 7. A D-isomer of a compound according to claim
 1. 8.Acetone O-[2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]-propionyl oxime. 9.EthylO-[2-[p-[(6-bromo-quinolyl)oxy]phenoxy]-propionly]acetohydroxamate. 10.[(Isopropylideneamino)oxy]methyl2-[p-[6-fluoro-2-quinolyl)oxy]phenoxy]propionate.
 11. The D-isomers ofthe compounds according to any one of claim 8, 9 or
 10. 12. A herbicidalcomposition which comprises an inert carrier material, and as the activeingredient, an amount of one or more of the compounds of claim 1 whichis effective as a herbicide.
 13. A herbicidal composition of claim 12,wherein the active ingredient is AcetoneO-[2-[p-[(6-chloro-2-quinolyl)oxy]phenoxy]-propionyl oxime.
 14. Aherbicidal composition of claim 12 where the active ingredient is EthylO-[2-[p-[(6-bromo-quinolyl)oxy]phenoxy]-propionyl]acetohydroxamate. 15.A herbicidal composition of claim 12 where the active ingredient is[(Isopropylideneamino)oxy]methyl2-[p-[(6-fluoro-2-quinolyl)oxy]phenoxy]propionate.
 16. A method forcombatting weeds which comprises applying, to the locus to be protected,a herbicidally effective amount of the composition of claim
 12. 17. Amethod for combatting weeds which comprises applying, to the locus to beprotected, a herbicidally effective amount of the composition of claim13.
 18. A method for combatting weeds which comprises applying, to thelocus to be protected, a herbicidally effective amount of thecomposition of claim
 14. 19. A method for combatting weeds whichcomprises applying, to the locus to be protected, a herbicidallyeffective amount of the composition of claim
 15. 20. An oxime ester ofthe formula ##STR17## wherein A is ##STR18## in which R₃ is hydrogen,halogen or trifluoromethyl, m is 1 or 2, B is --CH═, and wherein R₁ is agroup of the formula ##STR19## wherein R₆ and R₇ are lower alkyl,cycloalkyl with 3 to 6 carbon atoms, lower alkylcarbonyloxy-lower alkyl,lower alkoxy or lower alkylthio or R₆ and R₇ together with the carbonatom to which they are attached are a cycloalkyl group with 3 to 7carbon atoms, and wherein n is 1 or 2, and wherein R₆ can also behydrogen.